TW201522538A - 新穎塗料組合物 - Google Patents
新穎塗料組合物 Download PDFInfo
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- TW201522538A TW201522538A TW103134666A TW103134666A TW201522538A TW 201522538 A TW201522538 A TW 201522538A TW 103134666 A TW103134666 A TW 103134666A TW 103134666 A TW103134666 A TW 103134666A TW 201522538 A TW201522538 A TW 201522538A
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Abstract
本發明係關於一種塗料組合物,其包含:a)包含二級胺基之成膜樹脂,b)聚異氰酸酯固化劑,及c)以胺基樹脂為主之聚合物固體粒子。
Description
本發明係關於VOC低(低於250g/l)、乾燥快速且抗蝕性極佳之保護塗料組合物。此等塗料組合物尤其適用於塗佈風機葉片。
風力使用風力渦輪機將風能轉化成諸如電之適用形式。風力產生於與電網連接之大規模風力農場以及獨立渦輪機中用於將電提供至分離之位置。風力渦輪機通常具有2至4個經設計以持續約20年至25年之大葉片。風力渦輪機葉片或「風機葉片」連續暴露於自然環境,且其經理想設計以經受極限溫度、風切、沈澱及/或其他環境危害而故障最少。在葉片前邊緣上常常觀測到因侵蝕所致之塗料失效。葉片之「前邊緣」應理解為指葉片首先切入風中之部分,而後邊緣則為相對邊緣。前邊緣通常經歷諸如鹽、砂、塵土及其他造成乾磨蝕之粒子的環境因素,以及諸如風、雨、雪及其類似物之濕潤環境因素。因此,在前邊緣上可觀測到加速之塗料失效及/或侵蝕。
因此,用於風機葉片上之保護塗料必須符合極嚴格之標準以便其持續其約20-25年之壽命。在與諸如風機葉片之基材衝撞期間,水滴顯著改變其形狀。大部分時間,雨滴在塗膜表面上產生類似衝擊波之漣波,而僅在漣波之震央造成很小損害。對欲長期經受住雨滴多次衝撞的風機葉片上之塗料而言,塗膜應具有針對基材之優良黏著性及優良之回彈性。
目前用於塗佈風機葉片之主要市售產品為以聚酯為主之聚胺甲
酸酯。儘管此等塗料產品具有合理之黏著性及抗性特性,但其高揮發性有機物含量(Volatile Organic Content,VOC)均高於250g/l,且在環境溫度下常常乾燥緩慢。為了提高此等塗料之乾燥速率,可將其在空氣烘箱中加熱。另外,風機葉片上常常需要聚胺甲酸酯塗料之多層塗料以獲得所需之雨蝕保護。將多層塗料塗覆於風機葉片耗時且昂貴。相比而言,本發明之塗料組合物能夠在基材表面初步處理程度最低之情況下很容易地以一個塗層塗覆至基板,且此塗層提供優良之雨蝕保護。
包含聚脲型樹脂之塗料組合物,例如由聚天冬胺酸酯胺及異氰酸酯固化劑形成之組合物在保護塗料產業中為已知的。然而,已知該等塗料之抗蝕性不及市售主要的以聚酯為主之聚胺甲酸酯系統優良。意外地,本發明人已發現當將以胺基樹脂為主之聚合物添加至聚脲塗料系統中時,該塗料之抗蝕性大大提高至以下程度,即本發明之塗料所提供的抗蝕性至少與主要之以聚酯為主之聚胺甲酸酯塗料系統的抗蝕性一樣優良。然而,本發明之聚脲塗料不僅確實提供優良抗蝕性,而且有利的是,與主要的以聚酯為主之聚胺甲酸酯塗料系統相比,其VOC亦較低。另外,本發明之塗料組合物能夠以較少塗層(例如僅一個塗層)提供相同保護,且能夠使用標準技術塗覆。本發明之塗料能夠在風力渦輪機葉片所經歷的尤其惡劣之雨蝕條件下提供保護。
本發明提供之塗料組合物VOC低(較佳為低於250g/l),在環境條件(較佳為不到3小時,在50% RH及25℃下)中乾燥時間短,適用期良好(例如在25℃下90min或更長),且可使用標準技術容易地塗覆。另外,與已知以聚脲為主之塗料系統相比,該塗料所提供之優越侵蝕保護(尤其雨蝕保護)可僅以一個塗層實現。
本申請案係關於一種塗料組合物,其包含:
a)包含二級胺基之成膜樹脂,b)聚異氰酸酯固化劑,及c)以胺基樹脂為主之聚合物固體粒子。
較佳地,(a)及(b)以如下量存在於塗料組合物中:異氰酸酯基:二級胺基之化學計量比率為1.0:1.0至2.5:1.0。
包含二級胺基之成膜樹脂可為聚天冬胺酸酯胺。
以胺基樹脂為主之聚合物可為以甲基脲為主之聚合物。以胺基樹脂為主之聚合物可為交聯之聚合物。以整個塗料組合物之重量計,以胺基樹脂為主之聚合物固體粒子一般以1重量%至25重量%之量存在。
聚異氰酸酯固化劑之異氰酸酯當量可在280g/cq與840g/eq之間,例如在280g/eq與500g/eq之間。
包含二級胺基之成膜樹脂的胺當量可在150g/eq與450g/eq之間。
較佳地,(a)及(b)以如下量存在於塗料組合物中:異氰酸酯基:二級胺基之化學計量比率為大於1.2:1.0、大於1.3:1.0且較佳大於1.5:1.0,最高比率為2.5:1.0。
本發明利用已知聚天冬胺酸酯胺。在一個實施例中,聚天冬胺酸酯胺具有以下通式結構:
其中X表示在高達100℃之溫度下對異氰酸酯基具有惰性之脂環烴;
R1及R2係各自獨立地選自在高達100℃之溫度下對異氰酸酯基具有惰性之有機基;R3及R4係各自獨立地選自氫及在高達100℃之溫度下對異氰酸酯基具有惰性之有機基;及n為至少2之整數。
塗料組合物通常以兩個包裝提供,第一包裝包含聚天冬胺酸酯胺且第二包裝包含聚異氰酸酯固化劑。
本發明亦係關於一種保護基材不受侵蝕(例如雨蝕或固體粒子侵蝕)之方法,其藉由以下步驟實現:- 提供如本文所述之塗料組合物(例如,包括包含二級胺基之成膜樹脂、聚異氰酸酯固化劑及以胺基樹脂為主之聚合物固體粒子的塗料組合物),- 將塗料組合物塗覆至基材以在基材上形成一或多個塗層,及- 使該(等)塗層於環境溫度下在基材上硬化/固化。
本發明之塗料組合物可例如僅以一個塗層在約100μm至約300μm之厚度下塗覆。
基材可為風機葉片或其一部分。侵蝕可為固體粒子侵蝕或雨蝕。能夠在環境溫度下硬化/固化之塗料組合物為不需要人工加熱以實現固化/硬化之塗料組合物。因此,一旦在無額外加熱之情況下塗覆本發明之塗料組合物,其即能夠在基材上固化以形成塗膜。此項技術中通常亦為已知之環境溫度為0℃至30℃之範圍內的溫度。
本發明亦係關於經塗佈之基材,例如風機葉片或其一部分,其中該基材塗佈有本文所述之塗料組合物。
本發明亦係關於以胺基樹脂為主之聚合物固體粒子在在塗料組合物中之用途,其用於改良由該塗料組合物形成之塗料的抗雨蝕性或抗固體粒子侵蝕性。
可根據ASTM G73-10量測抗雨蝕性之改良。可根據用於粒子侵蝕測試之ASTM G76量測抗固體粒子侵蝕性之改良。
包含二級胺基之成膜樹脂之適合實例包括例如脂族聚酯胺、脂族聚醚胺及聚天冬胺酸酯胺。
包含二級胺基之成膜樹脂之數目平均分子量較佳在500g/mol與1200g/mol之間,例如550g/mol與900g/mol之間的範圍內。可根據ISO 13885-1:2008藉由GPC量測分子量。
包含二級胺基之成膜樹脂的胺當量可在150g/eq與450g/eq之間,例如200-350g/eq。
胺當量按照下式自胺值計算:胺當量=56.1×1000/[胺值],其中胺值可根據ASTM D 2074測定。
較佳之包含二級胺基之成膜樹脂為諸如描述於美國專利第5,126,170號中且對應於以下通式(I)之彼等者的聚天冬胺酸酯胺:
其中X表示在高達100℃之溫度下對異氰酸酯基具有惰性之脂環烴;R1及R2係各自獨立地選自在高達100℃之溫度下對異氰酸酯基具
有惰性之有機基;R3及R4係各自獨立地選自氫及在高達100℃之溫度下對異氰酸酯基具有惰性之有機基;及n為至少2之整數。
舉例而言,X可為包含6至20個碳原子之脂環烴。較佳地,X表示藉由自以下移除胺基所獲得之二價烴基:1,4-二胺基丁烷、1,6-二胺基己烷、2,2,4-及2,4,4-三甲基-1,6-二胺基己烷、1-胺基-3,3,5-三甲基-5-胺甲基-環己烷、4,4'-二胺基-二環己基甲烷或3,3-二甲基-4,4'-二胺基-二環己基甲烷。
較佳地,n為2。
較佳地,R1及R2表示C1-C6烷基,例如甲基或乙基。較佳地,R3及R4表示氫。
如美國專利第5,126,170號中所描述,可藉由使包含一級胺基之一或多種環狀多元胺與不飽和二烷酯反應來製備聚天冬胺酸酯胺。
用於製造聚天冬胺酸酯的包含一個以上一級胺基之環狀多元胺組分通常包含6至25個碳原子,且含有至少一個脂環族環。適合之脂環族二胺組分之實例包括1,3-二胺基環己烷,1,4-二胺基環己烷,1,6-二胺基環己烷,2,2,4-及2,4,4-三甲基-1,6-二胺基己烷,1-胺基-3,3,5-三甲基-5-胺基甲基己烷且較佳為包括1,3-雙(胺基甲基)環己烷、1,4-雙(胺基甲基)環己烷之雙(胺基甲基)環己烷,異佛爾酮二胺,雙(4-胺基環己基)甲烷,雙(4-胺基環己基)丙烷,4,4-二胺基-3,3-二甲基二環己基甲烷,4,4-二胺基-3,3-二甲基二環己基丙烷,4,4-二胺基-3,3-二甲基-5,5-二甲基二環己基甲烷,4,4-二胺基-3,3-二甲基-5,5-二甲基二環己基丙烷。
用於製造聚天冬胺酸酯之不飽和二烷酯較佳為丁烯二酸二乙酯,例如順丁烯二酸或反丁烯二酸之酯,例如順丁烯二酸及反丁烯二
酸之二甲酯、二乙酯、二丙酯及二正丁酯。
或者,聚天冬胺酸酯可對應於通式(I),然而其中X為包含5至10個碳原子之脂族二價烴基而R1、R2、R3、R4及n與上述定義相同。
舉例而言,X可表示藉由自2-甲基戊烷二胺或己二胺移除胺基所獲得之二價烴基。可藉由使包含一級胺基之一或多種脂族多元胺與不飽和二烷酯(如上所述)反應來製備聚天冬胺酸酯。
可用於本發明之聚天冬胺酸酯之一實例為Desmophen® NH1420(購自Bayer Material Science AG)。
如先前所提及,包含二級胺基之成膜樹脂之其他適合實例包括例如脂族聚酯胺及脂族聚醚胺。脂族聚醚胺之市售實例包括JEFFAMINE® SD-二級聚醚胺,諸如JEFFAMINE® SD-231胺、JEFFAMINE® SD-401胺、JEFFAMINE® SD-2001胺,其均來自HuntsmanCorporation。
聚異氰酸酯固化劑可為一或多種聚異氰酸酯固化劑。
一或多種聚異氰酸酯固化劑之異氰酸酯當量之範圍可在280g/eq與1500g/eq之間,例如280g/eq至1200g/eq或280g/eq至840g/eq。
異氰酸酯當量(isocyanate equivalent weight,「NCO eq.wt」)意謂1當量異氰酸酯(isocyanate,「NCO」)反應基所需產物之公克數目。
異氰酸酯當量(g/eq)=4,200/[聚異氰酸酯之NCO重量%]。舉例而言,若已知聚異氰酸酯固化劑之NCO重量%為10,則所計算出之異氰酸酯當量為4,200/10=420g/eq。可根據ASTM D2572-87藉由使用二正丁胺之滴定法來量測聚異氰酸酯組分之異氰酸酯基含量。
在全部實施例中,異氰酸酯當量可為大於300g/eq,或大於320g/eq,或大於340g/eq。
在全部實施例中,聚異氰酸酯固化劑之異氰酸酯當量可為小於
1500g/eq,或小於1200g/eq、840g/eq、800g/eq、750g/eq、700g/eq、650g/eq、600g/eq、550g/eg或500g/eq。
舉例而言,聚異氰酸酯固化劑之異氰酸酯當量為280g/eq至1500g/eq,280g/eq至1200g/eq,280g/eq至840g/eq,300g/eq至1500g/eq,300g/eq至1200g/eq,300g/eq至800g/eq,300g/eq至700g/eq,300g/eq至600g/eq,300g/eq至500g/eq,350g/eq至1500g/eq,350g/eq至1200g/eq,350g/eq至840g/eq,或350g/eq至450g/eq。
另外,聚異氰酸酯固化劑之數目平均分子量之範圍可在550g/mol與2000g/mol之間,例如1000g/mol至2000g/mol或1200g/mol至1800g/mol。可根據ISO-13885-1:2008藉由GPC量測分子量。
一或多種聚異氰酸酯固化劑可選自一或多種芳族或脂族聚異氰酸酯。該等聚異氰酸酯包括如二異氰酸酯及三異氰酸酯,包括縮二脲及異氰尿酸酯。較佳為聚異氰酸酯固化劑包含至少一種脂族聚異氰酸酯固化劑。較佳地,脂族聚異氰酸酯係基於六亞甲基二異氰酸酯。
二異氰酸酯包括甲苯二異氰酸酯,4,4'-亞甲基-雙(異氰酸環己酯),異佛爾酮二異氰酸酯,2,2,4-及2,4,4-三甲基六亞甲基二異氰酸酯之異構混合物,1,6-六亞甲基二異氰酸酯,四甲基二甲苯基二異氰酸酯及/或4,4'-二苯基亞甲基二異氰酸酯。
二異氰酸酯之縮二脲包括1,4-伸丁基二異氰酸酯及1,6-六亞甲基二異氰酸酯,以及環脂族二異氰酸酯,諸如異佛爾酮二異氰酸酯及4,4'-亞甲基-雙(異氰酸環己酯)之縮二脲。可自其製備縮二脲之二異氰酸芳烷酯之實例為間二甲苯基二異氰酸酯及α.,.α.,.α.',.α.'-四甲基間二甲苯基二異氰酸酯。
三官能異氰酸酯包括異佛爾酮二異氰酸酯、三異氰酸酯基壬烷、三苯基甲烷三異氰酸酯、1,3,5-苯三異氰酸酯、2,4,6-甲苯三異氰
酸酯及六亞甲基二異氰酸酯之異氰尿酸酯的三聚體。尤其使用之聚異氰酸酯為脂環族異氰酸酯,特定言之,為二異氰酸酯,諸如六亞甲基二異氰酸酯及異佛爾酮二異氰酸酯之異氰尿酸酯。
聚異氰酸酯固化劑可為一或多種聚異氰酸酯預聚物。聚異氰酸酯預聚物為此項技術中已知的。其為藉由使多元醇與過量二異氰酸酯單體反應而產生的離散分子。用於本發明的適合聚異氰酸酯預聚物之實例為六亞甲基二異氰酸酯之聚異氰酸酯預聚物。該等適合之聚異氰酸酯預聚物可自例如Bayer Corporation之Desmodur® N3800及Desmodur® E3370商購獲得。Desmodur® N3800為脂族聚異氰酸酯(HDI異氰尿酸酯三聚體),其NCO含量為11±0.5%(異氰酸酯當量=4,200/11=382g/eq)。Desmodur®E3370為亦基於六亞甲基二異氰酸酯之脂族聚異氰酸酯預聚物,其NCO含量為10.0±0.5%(異氰酸酯當量=4,200/11=400g/eq)。此等聚異氰酸酯預聚物可單獨或彼此組合使用。
異氰酸酯基與二級胺基的「1:1之化學計量比率」應以其通常方式理解為:存在相等數量之異氰酸酯基與二級胺基。
包含二級胺基之成膜樹脂(例如聚天冬胺酸酯胺)及聚異氰酸酯固化劑較佳以如下量存在於塗料組合物中:異氰酸酯基(NCO):二級胺基(NR2H)之化學計量比率為1.0:1.0至2.5:1.0。(亦即1.0至2.5異氰酸酯基比每1.0二級胺基)。
組分(a)及(b)可以如下量存在於塗料組合物中:異氰酸酯基:二級胺基之化學計量比率為大於1.3:1.0,大於1.4:1.0,大於1.5:1.0及宜大於1.6:1.0,達至最高之化學計量比率2.5:1.0。
異氰酸酯基:二級胺基之化學計量比率可為最高2.4:1.0、2.3:1.0、2.2:1.0、2.1:1.0或1.9:1.0。
塗料組合物包含以胺基樹脂為主之聚合物固體粒子。
基於塗料組合物之總重量計算,以胺基樹脂為主之聚合物固體粒子可以如下量存在於塗料組合物中:至少1重量%,或至少2重量%,抑或至少4重量%。基於組合物之總重量計算,粒子量之上限宜為25重量%,或20重量%,或14重量%。平均粒徑一般在1μm至150μm之範圍內。所使用之粒子一般具有粒徑分佈。舉例而言,全部粒子之90%可小於14μm,且全部粒子之50%可小於6.5μm。粒徑可用雷射繞射法量測,例如藉由使用Horiba雷射繞射粒徑分析器。
粒子之橫向尺寸及縱向尺寸可為類似數量級。粒子基本上可例如為球形。然而,粒子亦可具有其他形狀,例如薄片狀或針狀。
以胺基樹脂為主之聚合物宜藉由胺基樹脂或胺基樹脂前驅物與甲醛之縮合反應或藉由胺之其他縮合及/或加成反應製備。適合之以胺基樹脂為主之聚合物的實例為以胍為主之聚合物,以三聚氰胺為主之聚合物,以胺基甲酸酯為主之聚合物,以醯胺為主之聚合物,及以脲為主之聚合物,特定言之以甲基脲為主之聚合物。以胺基樹脂為主之聚合物宜為交聯的,亦即該聚合物為脲醛(duroplast)。交聯可在胺基樹脂與甲醛之縮合反應中進行。然而,交聯亦可由額外之交聯劑引起。適合之以胺基樹脂為主之聚合物固體粒子為例如以商標名Deuteron® MK購自Deuteron GmbH,Germany。Deuteron® MK粒子係基於甲基脲聚合物。
塗料組合物通常包含溶劑。可使用的溶劑之實例包括例如二甲苯,脂族白色石油腦(white spirit)溶劑,礦油精,諸如以下C3-C8酮溶劑之酮溶劑:甲基異戊基酮、甲基正丁基酮、甲基異丁基酮、甲基乙基酮、二乙基酮及丙酮,及諸如以下乙酸酯之酯溶劑:乙酸乙酯、乙
酸丙酯、乙酸丁酯及乙酸1-甲氧基-2-丙酯。塗料組合物中可使用一或多種溶劑。
塗料組合物亦可包括各種其他填料及添加劑,例如顏料、展延顏料、著色劑、顏料分散劑、腐蝕抑制劑、強化劑、流變控制劑、均染劑、賦脂劑、濕潤劑、抗縮孔劑、消泡劑、殺生物劑、促進劑、界面活性劑、(有機)溶劑、塑化劑、輕型穩定劑、UV光吸收劑(例如Tinuvin® 292)、濕氣清除劑、抗氧化劑及惡臭掩蔽劑。
填料為一種溶劑不可溶之固體物質,其通常用以在不損害塗料混合物(例如顏料及展延顏料)之反應化學性質的情況下增加總體積或用以擴展顏料之能力。填料可以塗料組合物總重量之2重量%至30重量%之濃度採用。
亦可包括填料以抑制腐蝕或提供強度。填料之實例包括細微粉碎之礦物,諸如硫酸鋇、包括煙霧狀二氧化矽及/或膠態二氧化矽之二氧化矽、氧化鋁、高嶺土、膠態氧化鋁、二氧化鈦、氧化鋯、膠態氧化鋯、黏土、雲母、白雲石、滑石、碳酸鎂、碳酸鈣、硫酸鈣、矽酸鈣及/或偏矽酸鈣。其他填料包括陶瓷微球與空心聚合微球,諸如以商品名Expancel®購自Akzo Nobel之彼等者,及空心玻璃微球(諸如以商標名「K37」TM購自3M Company,St.Paul,Minn之彼等者)。
塗料組合物可包括著色劑。如本文中所使用,術語「著色劑」意謂對組合物賦予顏色及/或其他不透明度及/或其他視覺效果之任何物質。著色劑可以諸如離散粒子、分散液、溶液及/或薄片之任何適合形式添加至塗料中。單種著色劑或者兩種或兩種以上著色劑之混合物可用於本發明之塗料中。
著色劑之實例包括顏料、染料及色彩,諸如油漆工業中所使用及/或乾顏料製造商協會(the Dry Color Manufacturers Association,
DCMA)中所列之彼等者以及特殊效果組合物。著色劑可包括例如不可溶但可在使用條件下濕潤的細微粉碎之固體粉末。著色劑可為有機的或無機的,且可為聚結的或非聚結的。著色劑可藉由研磨或簡單混合併入塗料中。著色劑可藉由使用研磨媒劑(諸如丙烯酸研磨媒劑)進行研磨而併入塗料中,研磨媒劑之使用應為熟習此項技術者所熟悉。著色劑可藉由使用色料/顏色濃縮物併入。
本發明之典型塗料組合物包含:˙5重量%至30重量%包含二級胺基之成膜樹脂,例如聚天冬胺酸酯胺;˙20重量%至50重量%聚異氰酸酯固化劑,及˙5重量%至20重量%以胺基樹脂為主之聚合物固體粒子。
塗料組合物亦可包含5重量%至20重量%鋁矽酸鹽。
鋁矽酸鹽為由鋁、矽及氧加相對離子構成之礦物。其為高嶺土及其他黏土礦物之主要組分。紅柱石、藍晶石及矽線石為天然存在之具有Al2SiO5組成之鋁矽酸鹽礦物。水合鋁矽酸鹽礦物稱為沸石且為具有多孔結構的天然存在之材料。
本發明之典型塗料組合物包含:˙5重量%至30重量%包含二級胺基之成膜樹脂,例如聚天冬胺酸酯胺;˙20重量%至50重量%聚異氰酸酯固化劑,及˙5重量%至20重量%以胺基樹脂為主之聚合物固體粒子,˙15重量%至30重量%一或多種顏料及/或展延顏料,˙10重量%至30重量%一或多種有機溶劑。
典型塗料組合物亦可包含1重量%至10重量%一或多種未列於上文之其他添加劑,例如用於輔助濕潤、分散、均染、流動、吸收
UV(例如Tinuvin® 292)、減少變形之添加劑及搖變劑(例如膨潤土搖變劑)。
除非另外陳述,否則塗料組合物中各組分之重量%係以包括溶劑之塗料組合物中組分之總重量計。
塗料組合物可藉由通常在生產油漆之技術領域內使用的任何適合技術製備。因此,可使用高速分散器、球磨機、珠磨機、三輥研磨機、砂磨機、籃式研磨機等將各種組分混合在一起。可使用袋濾器、保護過濾器(patron filter)、線隙過濾器(wire gap filter)、楔形網過濾器(wedge wire filter)、金屬邊緣過濾器(metal edge filter)、EGLM turnoclean過濾器(購自Cuno)、DELTA應力過濾器(購自Cuno)及Jenag Strainer過濾器(購自Jenag)或藉由振動過濾來過濾本發明之油漆。
本發明之塗料組合物通常以兩包裝組合物之形式提供,一個包裝中為包含二級胺基之成膜樹脂且另一個包裝中為聚異氰酸酯固化劑。以胺基樹脂為主之聚合物固體粒子亦通常在含有聚天冬胺酸酯之包裝中。在塗覆塗料組合物之前,將兩個包裝混合在一起。
塗料組合物可藉由包括以下之多個方法中的一或多者塗覆至基材:噴塗、輥壓、簾式塗佈、浸漬/浸沒、刷塗或流動塗佈,但塗料組合物最常藉由噴塗及輥壓塗覆。常見噴塗技術及設備為空氣噴塗及靜電噴塗,且可為手動或自動方法。舉例而言,可使用機械噴塗方法。
塗料組合物通常在環境溫度下固化。能夠在環境溫度下固化之塗料組合物為不需要人工加熱以實現固化之塗料組合物。因此,一旦在無額外加熱之情況下塗覆本發明之塗料組合物,其即能夠在基材上固化以形成塗膜。此項技術中通常亦為已知之環境溫度為0℃至30℃
之範圍內的溫度。
塗料組合物又可在低烘烤條件下固化以加速固化(例如,高於30℃至約35℃)。本發明之塗料組合物之優點為其(i)具有能夠使用習知技術(例如,標準無空氣/空氣輔助設備)將其塗覆之適用期,且(ii)其可在環境溫度下快速固化。若利用環境溫度固化,則對組合物而言在50%相對濕度(50% RH)及25℃下不到3小時固化為可能的。組合物常常在50%相對濕度(50% RH)及25℃下不到2小時固化。
風機葉片通常由複合材料製成。「複合物」一般應理解為係指由兩種或兩種以上不同材料製造之工程材料。通常,該兩種或兩種以上材料具有不同(有時顯著不同)之物理及/或化學特性。複合物通常具有基質材料及強化材料;基質材料包圍且支撐強化材料。本發明之複合物通常包含聚合材料作為基質材料及纖維作為強化材料。纖維可包含例如玻璃纖維(亦即纖維玻璃)、碳纖維、芳族聚醯胺纖維、克維拉(Kevlar)纖維、由天然材料製造之纖維及由奈米粒子製造之纖維。適合聚合材料可為熱塑性或熱固性的且包括例如聚酯及環氧樹脂。通常,纖維中之至少一者應至少部分塗佈有聚合材料或嵌入聚合材料中。特定實例包括纖維強化型複合材料,諸如強化型玻璃纖維複合物,其尤其適用於風機葉片結構。諸如塑膠之纖維強化型聚合物亦在如本文所使用之術語「複合物」之範疇內。本發明之複合物基材可具有一個連續表面,諸如兩個相對表面之兩個或兩個以上表面,或任何其他組態。在一特定實施例中,基材為呈風機葉片形式之複合物。
塗料系統可塗覆至複合物之至少一部分,例如塗覆至風機葉片之前邊緣。
在複合物表面上沈積任何塗料組合物之前,通常需要藉由澈底清潔且必要時對該表面除油來自該表面移除外來物質。該等清潔通常在使基材成形(例如,藉由模製)為最終使用形狀之後進行。基材表面
可藉由物理或化學手段或兩者來清潔,諸如機械摩擦該表面(例如噴砂清潔)或用熟習此項技術者所熟知的市售之鹼性或酸性清潔劑,諸如偏矽酸鈉及氫氧化鈉來清潔/除油。
清潔步驟之後,可用去離子水或漂洗劑之水溶液漂洗基材以移除任何殘留物。可例如藉由使用氣刀,藉由使基材短暫暴露於高溫以閃蒸掉水,或藉由使基材在壓輥之間穿過來風乾基材。為了使表面準備(光滑度)達至最佳,可塗覆油灰/填料以填充表面缺陷。已知適用於航空及汽車基材初步處理或修復之領域的油灰組合物及塗料為適於使用的。油灰通常用刀片手工塗覆且經砂磨以獲得可接受之光滑表面。氣刀亦可用於由砂磨移除殘留物。
本發明之塗料組合物之一個優點為其適於用作底漆塗層及頂塗層。此意謂僅需要一層塗料組合物來塗佈風機葉片。有利的是,塗料組合物能夠僅以一個塗層以約100μm至約300μm之乾膜厚度塗覆。塗層數量減少使得進行風機葉片維護所需時間較少,且無本發明之風機葉片塗層與任何其他塗層之相容性問題。
準備塗覆之塗料組合物之黏度應適合於使用標準塗覆技術進行塗覆。舉例而言,根據ASTM D4287所量測,準備塗覆之塗料組合物之黏度較佳為25℃下在0.1泊與10泊之間。
本發明之塗料組合物亦可用於修復風機葉片之方法中。用於修復風機葉片之方法應包含將本申請案之塗料組合物塗覆至風機葉片之至少一部分的步驟。塗料可實質上塗覆至風機葉片之所有部分,或僅塗覆至風機葉片之一部分,諸如風機葉片之前邊緣。在某些實施例中,塗層中之一或多者可塗覆至風機葉片之至少一部分。以此方式修復之風機葉片可具有預先存在之塗料或塗層,其一些或全部可在塗覆頂塗層之前移除。或者,新增之頂塗層可在存在之塗層上方塗敷且將為「第二」頂塗層。在此實施例中,可將連接塗層或其他促進黏著之
層塗覆至存在之塗層。
本文所揭示之塗料組合物尤其適於在風機葉片上使用以保護風機葉片不受雨蝕,然而其亦可用於保護風機葉片及其他基材不受固體粒子侵蝕。其他應用之實例包括採礦及建築產業中之使用,及用作土工設備上原始設備製造商(original equipment manufacturer,OEM)面漆。
因此,本發明係關於本文所揭示之塗料組合物之用途,其用於塗佈基材,尤其當需要保護基材不受例如水/雨蝕及固體粒子侵蝕之侵蝕時。
基材包括諸如金屬、混凝土及塑膠之材料,或此等已塗佈有或部分塗佈有油漆或填料之材料。油漆可為例如本發明之塗料或包含以聚脲(例如芳族或脂族聚天冬胺酸樹脂)、聚胺甲酸酯或環氧為主的樹脂之不同塗料。有利的是,塗料組合物可直接塗覆至上述材料。
本發明亦係關於塗佈有本發明之塗料組合物的此等基材。
以下實例意欲說明本發明之各種實施例,且不應解釋為以任何方式限制本發明。
實例1及實例2塗料組合物係藉由使用高速分散器及砂磨機將表1中之組分1至組分9混合在一起來製備。組分1至組分7首先混合在一起,隨後添加預混之組分8及組分9。異氰酸酯基:二級胺基之化學計量比率為1.8:1。
除實例1中以胺基樹脂為主之聚合物粒子在實例2中用習知之填充材料滑石(水合矽酸鎂)替換以外,用於調配實例1及比較實例2之全部組分為相同的。
與實例1相同,實例2及實例3中異氰酸酯基:二級胺基之化學計量
比率為1.8:1。
藉由噴塗技術將各實例之塗料組合物以200μm之乾膜厚度塗覆至由玻璃強化型環氧複合物基材製造的翼形模具且使其在27℃下固化。隨後,使測試塗料持續21天成熟作用以發展完整之薄膜特性。
根據ASTM G73-10測定各塗料之抗雨蝕性。此測試涉及將測試樣本附接至旋轉臂,使得測試樣本在其環形路徑中反覆通過水噴霧且受到水噴霧衝擊。其為加速測試方法,其中測試極高速度下樣本對多次水滴衝擊之抗性。在此加速測試中展示良好效能之塗料預期在技術領域中具有良好耐久性。
測試參數:
測試持續時間 3小時
葉片長度 22cm
葉片根部速度 126m/sec
葉片中部速度 143m/sec
葉片端部速度 160m/sec
雨 30mm/hour至33mm/hour
雨滴大小 1mm至2mm
溫度 20℃至25℃
抗雨蝕性的評估係基於因雨滴之重複多次衝擊所致的對塗料之可見損害之量。每30分鐘以肉眼評估塗料,持續3小時。就全部塗料而言,最初損害均在速度最大之葉片端部。在測試期間,亦發現對塗料之損害逐漸向上延伸至葉片之根部。與抗雨蝕性較低之塗料相比,抗雨蝕性較高之塗料受損面積之長度較短。
雨蝕測試之結果展示於表2中。
* 最大可能之損害長度為22cm。
比較實例2之塗料在僅1小時之後沿葉片之整個長度受損。然而,實例1之塗料具有極佳抗雨蝕性。實例1之塗料花費2.5小時(2.5倍長)才沿葉片之整個長度受損。與實例2之比較塗料相比,實例1之塗料具有優越之抗雨蝕性。
藉由BK乾燥軌道記錄器(ASTM D 5895)量測DFT為200微米的塗料硬乾之時間,其中改變為溫度/濕度為27℃,RH-78%。塗料之硬乾時間為130分鐘。作為比較,使用相同測試量測用於塗佈風機葉片的主要市售之以聚酯為主之聚胺甲酸酯產物的硬乾時間。發現主要市售之以聚酯為主之聚胺甲酸酯產物的乾燥時間為180分鐘。
根據EPA聯邦參考法(EPA Federal Reference Method)24測定塗料組合物1及比較塗料組合物2的揮發性有機物含量(VOC)。兩種塗料組合物之VOC低於250g/L。此顯著低於用於塗佈風機葉片的主要市售之以聚酯為主之聚胺甲酸酯產物,其VOC測定為420g/L。
Claims (15)
- 一種塗料組合物,其包含:a)包含二級胺基之成膜樹脂,b)聚異氰酸酯固化劑,及c)以胺基樹脂為主之聚合物固體粒子。
- 如請求項1之塗料組合物,其中(a)及(b)係以使得異氰酸酯基:二級胺基之化學計量比率為1.0:1.0至2.5:1.0之量存在於該塗料組合物中。
- 如請求項1之塗料組合物,其中該包含二級胺基之成膜樹脂為聚天冬胺酸酯胺。
- 如請求項1至3中任一項之塗料組合物,其中該以胺基樹脂為主之聚合物為以甲基脲為主之聚合物。
- 如請求項1至3中任一項之塗料組合物,其中該以胺基樹脂為主之聚合物為交聯之聚合物。
- 如請求項1至3中任一項之塗料組合物,其中以該整個塗料組合物之重量計,該等以胺基樹脂為主之聚合物固體粒子係以1重量%至25重量%之量存在。
- 如請求項1至3中任一項之塗料組合物,其中該聚異氰酸酯固化劑之異氰酸酯當量係在280g/eq與840g/eq之間,例如在280g/eq與500g/eq之間。
- 如請求項1至3中任一項之塗料組合物,其中該包含二級胺基之成膜樹脂的胺當量係在150g/eq與450g/eq之間。
- 如請求項1至3中任一項之塗料組合物,其中(a)及(b)係以使得異氰酸酯基:二級胺基之化學計量比率為大於1.5:1.0至最高比率為2.5:1.0之量存在於該塗料組合物中。
- 如請求項1至3之塗料組合物,其中該聚天冬胺酸酯胺具有以下結構:
- 如請求項1至3中任一項之塗料組合物,其中該塗料組合物係以兩個包裝提供,第一包裝包含該聚天冬胺酸酯胺且第二包裝包含該聚異氰酸酯固化劑。
- 一種保護基材不受雨蝕或固體粒子侵蝕之方法,其係藉由以下步驟達成提供如請求項1至11中任一項之塗料組合物,其包括包含二級胺基之成膜樹脂、聚異氰酸酯固化劑及以胺基樹脂為主之聚合物固體粒子,將該塗料組合物塗覆至該基材以在該基材上形成一或多個塗層,及使該(等)塗層於環境溫度下在該基材上硬化。
- 如請求項12之方法,其中該基材為風機葉片或其一部分。
- 一種經塗佈之風機葉片或其一部分,其中該風機葉片或其部分塗佈有如請求項1至11中任一項之塗料組合物。
- 一種以胺基樹脂為主之聚合物固體粒子於塗料組合物中之用途,其用於改良由該塗料組合物形成之塗料的抗雨蝕性或抗固體粒子侵蝕性。
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CN114846095B (zh) * | 2019-12-18 | 2023-08-29 | 乐金华奥斯有限公司 | 汽车涂膜保护用薄片及其制备方法 |
JP7324790B2 (ja) * | 2021-03-05 | 2023-08-10 | 日本ペイント・インダストリアルコーティングス株式会社 | 塗料組成物 |
CN113122120A (zh) * | 2021-04-21 | 2021-07-16 | 深圳市深赛尔股份有限公司 | 一种风电叶片涂料及其制备方法 |
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JPS61180924A (ja) * | 1984-12-28 | 1986-08-13 | Konishiroku Photo Ind Co Ltd | 磁気記録媒体 |
AU709278B2 (en) * | 1996-03-06 | 1999-08-26 | Rohm And Haas Company | Quick-drying aqueous coating compositions |
DE10300798A1 (de) * | 2003-01-13 | 2004-07-22 | Basf Coatings Ag | Mehrkomponentensystem und seine Verwendung zur Herstellung einer thermisch und mit aktinischer Strahlung härtbaren Triple-Cure-Mischung |
JP4523784B2 (ja) * | 2003-03-25 | 2010-08-11 | 日本ペイント株式会社 | 微小樹脂粒子含有o/w型エマルションを製造する方法、内部架橋した微小樹脂粒子含有o/w型エマルション、カチオン電着塗料組成物及び塗装物 |
KR20040084779A (ko) * | 2003-03-25 | 2004-10-06 | 닛뽕 뻬인또 가부시키가이샤 | 미소 수지 입자 함유 수중유 형 에멀전을 제조하는 방법,내부 가교한 미소 수지 입자 함유 수중유 형 에멀전,양이온 전착 도료 조성물 및 도장물 |
WO2006055038A1 (en) * | 2004-05-24 | 2006-05-26 | Hontek Corporation | Abrasion resistant coatings |
JP4634131B2 (ja) * | 2004-12-16 | 2011-02-16 | 関西ペイント株式会社 | アミノ樹脂水分散体組成物及び熱硬化性水性塗料組成物 |
TW200714985A (en) * | 2005-08-23 | 2007-04-16 | Fuji Photo Film Co Ltd | Optical sheet |
JP2010529246A (ja) * | 2007-06-05 | 2010-08-26 | アクゾ ノーベル コーティングス インターナショナル ビー ヴィ | 剥離可能な一時的コーティング |
NL1034986C2 (nl) * | 2008-02-01 | 2009-08-04 | Baril Coatings B V | Verfsamenstelling. |
CN102149741A (zh) * | 2008-09-12 | 2011-08-10 | 陶氏环球技术有限责任公司 | 基于多元胺、多元醇和多异氰酸酯的涂料配方和组合物及制备和使用它们的方法 |
ES2700868T3 (es) * | 2014-03-14 | 2019-02-19 | Akzo Nobel Coatings Int Bv | Composición de recubrimiento |
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2014
- 2014-10-01 WO PCT/EP2014/070998 patent/WO2015049260A1/en active Application Filing
- 2014-10-01 CA CA2925499A patent/CA2925499A1/en not_active Abandoned
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- 2014-10-01 RU RU2016116267A patent/RU2016116267A/ru not_active Application Discontinuation
- 2014-10-01 BR BR112016006626A patent/BR112016006626A2/pt active Search and Examination
- 2014-10-01 MX MX2016004029A patent/MX2016004029A/es unknown
- 2014-10-01 EP EP14781137.6A patent/EP3074442A1/en not_active Withdrawn
- 2014-10-01 AU AU2014331180A patent/AU2014331180B2/en not_active Expired - Fee Related
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RU2016116267A (ru) | 2017-11-10 |
KR20160065874A (ko) | 2016-06-09 |
JP2016539196A (ja) | 2016-12-15 |
AU2014331180B2 (en) | 2017-09-14 |
CA2925499A1 (en) | 2015-04-09 |
CN105593259A (zh) | 2016-05-18 |
EP3074442A1 (en) | 2016-10-05 |
SG11201602613VA (en) | 2016-04-28 |
AU2014331180A1 (en) | 2016-04-07 |
BR112016006626A2 (pt) | 2017-08-01 |
US20160244635A1 (en) | 2016-08-25 |
CN105593259B (zh) | 2018-04-13 |
US10030166B2 (en) | 2018-07-24 |
WO2015049260A1 (en) | 2015-04-09 |
MX2016004029A (es) | 2016-06-02 |
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